CN115738741B - Renewable acid-tolerant composite nanofiltration membrane, preparation method and application - Google Patents
Renewable acid-tolerant composite nanofiltration membrane, preparation method and application Download PDFInfo
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Abstract
The invention discloses a renewable acid-resistant composite nanofiltration membrane, a preparation method and application thereof, and relates to the technical field of membrane separation, wherein the preparation method of the composite nanofiltration membrane comprises the following steps: (1) preparing an oil phase solution by taking an oil phase monomer as a raw material; the oil phase monomer comprises polybasic acyl chloride and a compound containing triazine ring groups; (2) Preparing an aqueous phase solution by taking an aqueous phase monomer and a reducing agent as raw materials; the aqueous phase monomer is a phenolic compound, and the phenolic compound contains at least two hydroxyl groups or contains at least one hydroxyl group and amino group; (3) And carrying out interfacial polymerization on the oil phase solution and the water phase solution on the porous support membrane to obtain the renewable acid-resistant composite nanofiltration membrane. The composite nanofiltration membrane is provided with a supporting layer and a separating layer, rich reducing agent molecules are grafted on the surface and the inside of the separating layer, the composite nanofiltration membrane has good acid resistance and separation performance, can reduce heavy metal ions while consuming hydrogen ions, can be regenerated through simple reduction treatment, and has good reusability.
Description
Technical Field
The invention relates to the technical field of membrane separation, in particular to a renewable acid-resistant composite nanofiltration membrane, a preparation method and application.
Background
The acid wastewater containing heavy metals is commonly existing in industries such as steel processing, electronic product manufacturing and the like, and the traditional acid-base neutralization and oxidation treatment method needs to consume a large amount of medicaments, and meanwhile, the ion concentration in the wastewater can be increased, so that the resource utilization of the acid wastewater is not facilitated. In recent years, nanofiltration separation technology is widely applied to wastewater treatment, and unlike reverse osmosis technology for desalination, nanofiltration process can synchronously complete permeation of hydrogen ions and interception of multivalent metal ions, and is expected to realize resource utilization of acidic wastewater.
The separation layer of the traditional composite nanofiltration membrane is mainly aromatic polyamide, for example, chinese patent document with publication number of CN102133506A discloses a polyamide composite nanofiltration membrane, and the nanofiltration membrane is compounded with an ultrathin active separation layer on a porous support membrane through interfacial polycondensation between aqueous solution containing aliphatic macromolecular polyamine and organic solution containing binary aromatic reaction monomers. However, the carbonyl groups on the aromatic polyamide molecules are easy to undergo nucleophilic reaction with hydrogen ions, so that dissociation and chain scission are carried out, and finally the separation layer is separated from the support layer.
The triazine ring compound (cyanuric chloride and the like) shows stronger electron withdrawing capability due to the triazinone ring structure, and the electron cloud density on a polymer prepared by taking the triazine ring compound as a monomer is lower; is a very promising monomer for preparing the composite nanofiltration membrane. Chinese patent publication No. CN114130220a discloses a polytriazine alkali-resistant composite nanofiltration membrane, the separation layer of the composite nanofiltration membrane is formed by contact reaction of triazine compound containing more than two amine groups (primary amine or secondary amine) and a multifunctional crosslinking agent, and crosslinking by a post-crosslinking agent; however, the preparation of the composite nanofiltration membrane requires a post-crosslinking step, and the steps are more; the Chinese patent document with publication number CN107930412A discloses a preparation method of an acid-resistant poly (amide-triazine-amine) nanofiltration composite membrane, which comprises the steps of firstly taking cyanuric chloride and polyamine as raw materials, and obtaining a poly (triazine) amine precursor through nucleophilic substitution reaction; respectively preparing a poly (triazine) amine precursor aqueous phase reaction solution and a polybasic acyl chloride oil phase reaction solution, and preparing the nanofiltration composite membrane on a support membrane through interfacial polymerization reaction; however, the acid resistance of the nanofiltration composite membrane is poor, and the salt rejection rate of the membrane can be remarkably reduced with time.
Therefore, development of a nanofiltration membrane with high acid resistance and simple preparation process is urgently needed to meet the recycling treatment requirement of the heavy metal-containing acidic wastewater.
Disclosure of Invention
The invention provides a preparation method of a renewable acid-resistant composite nanofiltration membrane, which has the advantages of simple process, low equipment requirement, excellent acid resistance of the prepared composite nanofiltration membrane, good separation performance, capability of reducing heavy metal ions, reproducibility and good recycling effect.
The technical scheme adopted is as follows:
the preparation method of the renewable acid-resistant composite nanofiltration membrane comprises the following steps:
(1) Preparing an oil phase solution by taking an oil phase monomer as a raw material; the oil phase monomer comprises polybasic acyl chloride and a compound containing triazine ring groups;
(2) Preparing an aqueous phase solution by taking an aqueous phase monomer and a reducing agent as raw materials; the aqueous phase monomer is a phenolic compound, and the phenolic compound contains at least two hydroxyl groups or contains at least one hydroxyl group and amino group;
(3) And (3) carrying out interfacial polymerization on the oil phase solution in the step (1) and the aqueous phase solution in the step (2) on the porous support membrane to obtain the renewable acid-resistant composite nanofiltration membrane.
The invention takes polybasic acyl chloride and a compound containing triazine ring groups as oil phase monomers, and takes phenolic compounds containing at least two hydroxyl groups or at least one hydroxyl group and amino group as water phase monomers; in the interfacial polymerization film-making process, the polyacyl chloride has higher reactivity, can form a polymer network with water phase monomers through polycondensation reaction faster, and the compound containing triazine ring groups can also react with the water phase monomers to form acid-resistant ether bonds, so that the acid-resistant performance of the polymer network and even the film is enhanced; in addition, the reducing agent can be grafted on the surface and the inside of the membrane through the reaction with the oil phase monomer, and has certain reduction-regeneration characteristics, so that heavy metal ions can be reduced, meanwhile, hydrogen ions can be consumed, the damage of the hydrogen ions to a polymer network is further reduced, and the acid resistance of the composite membrane is further improved.
Preferably, the polybasic acyl chloride comprises trimesoyl chloride or isophthaloyl chloride; the compound containing triazine ring group comprises at least one of cyanuric chloride, 2, 4-dichloro-1, 3, 5-triazine or 2, 5-dichloro-1, 3, 5-triazine.
Further preferably, in the oil phase solution, the oil phase monomer is trimesoyl chloride and cyanuric chloride.
The aqueous monomer comprises at least one of resorcinol, bisphenol fluorene, 1-amino-5-naphthol or 1,1' -bi-2-naphthol.
Preferably, the reducing agent is sulfonated polyaniline, and the number average molecular weight is between 500 and 10000.
Preferably, in the oil phase solution, the mass concentration of the oil phase monomer is 0.5-5wt%; the mass ratio of the polybasic acyl chloride to the compound containing the triazine ring group is 0.1-10:1; in the aqueous phase solution, the mass concentration of the aqueous phase monomer is 2-8wt% and the mass concentration of the reducing agent is 0.02-1wt%; under the concentration range, the diffusion rate of the oil phase monomer and the water phase monomer at the water/oil two-phase interface is proper, and the prepared composite film has good integrity and compactness.
The porous support membrane includes, but is not limited to: cellulose acetate ultrafiltration membrane, polyethylene ultrafiltration membrane, polysulfone ultrafiltration membrane, polyamide ultrafiltration membrane, polyacrylonitrile ultrafiltration membrane, etc.
In the step (3), the interfacial polymerization reaction is carried out in two stages, wherein the parameters of the interfacial polymerization reaction in the first stage are that the reaction temperature is 20-40 ℃ and the reaction time is 1-20 minutes; in the first stage interfacial polymerization process, the main occurrence is the affinity substitution reaction between acyl chloride groups and hydroxyl and amino groups, and the first nucleophilic substitution reaction and the second nucleophilic substitution reaction on triazine rings; the parameters of the interfacial polymerization reaction in the second stage are that the reaction temperature is 60-90 ℃ and the reaction time is 5-20 minutes; in the second-stage interfacial polymerization, a third nucleophilic substitution reaction on the triazine ring and a reaction between the oil-phase monomer and the reducing agent mainly occur.
In the step (3), the oil phase solution in the step (1) and the aqueous phase solution in the step (2) are subjected to a first-stage interfacial polymerization reaction and a second-stage interfacial polymerization reaction on the porous support membrane to obtain the renewable acid-resistant composite nanofiltration membrane; or, after the oil phase solution in the step (1) and the water phase solution in the step (2) are subjected to a first-stage interfacial polymerization reaction on the porous support membrane, treating the obtained membrane with a reducing agent solution (sulfonated polyaniline solution) with the mass concentration of 2-8wt%, and then continuing to perform a second-stage interfacial polymerization reaction to obtain the renewable acid-resistant composite nanofiltration membrane.
When the membrane obtained after the first-stage interfacial polymerization reaction is treated by using the reducing agent solution with the mass concentration of 2-8wt%, the unreacted carbon-chlorine bonds on the surface of the membrane can be used for realizing the further grafting of the reducing agent, so that the reducing agent content on the surface of the membrane is enhanced, the reducing capability of the composite nanofiltration membrane on heavy metal ions is enhanced, and the damage of acidic wastewater on the composite nanofiltration membrane is further reduced.
Specifically, the interfacial polymerization process is as follows: contacting the surface of the porous support membrane with aqueous phase solution, standing and removing liquid drops on the surface of the membrane, and then placing the oil phase solution on the surface of the porous support membrane to perform first-stage interfacial polymerization reaction and second-stage interfacial polymerization reaction with the adsorbed aqueous phase solution; or, making the surface of the porous support membrane contact with the aqueous phase solution, standing and removing liquid drops on the surface of the membrane, and then placing the oil phase solution on the surface of the porous support membrane to perform a first-stage interfacial polymerization reaction with the adsorbed aqueous phase solution; 2-8wt% of reducer solution is coated on the surface of the membrane after the first-stage interfacial polymerization reaction, and then the second-stage interfacial polymerization reaction is continued.
The invention also provides the renewable acid-tolerant composite nanofiltration membrane prepared by the preparation method of the renewable acid-tolerant composite nanofiltration membrane, which is provided with a supporting layer and a separating layer, wherein rich reducing agent molecules are grafted on the surface and the inside of the separating layer.
The renewable acid-resistant composite nanofiltration membrane has excellent acid resistance and separation performance, has good reducibility to heavy metal ions (such as chromate ions), can be reused after being simply reduced and regenerated, and has excellent performance after regeneration.
Preferably, the renewable acid-tolerant composite nanofiltration membrane can be subjected to reduction regeneration by using a hydrazine hydrate solution, an ascorbic acid solution or a sodium citrate solution.
The invention also provides application of the renewable acid-resistant composite nanofiltration membrane in the field of wastewater treatment. When the renewable acid-tolerant composite nanofiltration membrane is used for treating acidic wastewater containing chromate ions, the retention rate of the renewable acid-tolerant composite nanofiltration membrane on the chromate ions is 90-98%, and the permeation flux is 10-15Lm -2 h -1 bar -1 Can realize the high-efficiency treatment of wastewater.
Compared with the prior art, the invention has the beneficial effects that:
(1) The invention takes the polybasic acyl chloride and the compound containing triazine ring groups as oil phase monomers, takes the phenolic compound containing at least two hydroxyl groups or at least one hydroxyl group and amino group as water phase monomers, combines the action of a reducing agent, and prepares the composite nanofiltration membrane with better acid resistance and separation performance, better heavy metal ion reduction performance and excellent regeneration and reuse performance; and the preparation method is simple, has low equipment requirement and is convenient for large-scale production.
(2) The renewable acid-tolerant composite nanofiltration membrane prepared by the method has good acid resistance, the separation performance of the membrane is still kept at a high level after acid treatment with the pH value of 1, the heavy metal ions can be reduced while the hydrogen ions are consumed, the method is very suitable for treating acid wastewater containing hexavalent chromium, and the regeneration can be realized through simple reduction treatment, and the reusability is good.
Drawings
FIG. 1 is an SEM image of a regenerable acid-resistant composite nanofiltration membrane prepared according to example 1.
Fig. 2 is an SEM image of the regenerable acid-tolerant composite nanofiltration membrane prepared in example 1 after acid treatment.
Detailed Description
The invention is further elucidated below in connection with the examples and the accompanying drawing. It is to be understood that these examples are for illustration of the invention only and are not intended to limit the scope of the invention.
The sulfonated polyaniline used in the examples is synthesized by copolymerizing aniline and metanilic acid with ammonium persulfate as an oxidizing agent (see, for specific Synthetic procedures, A. Sebenikbt Sulfonated polyaniline, synthetic Metals 101 (1999) 717-718, DOI:10.1016/S0379-6779 (98) 01166-7).
Example 1
(1) And (3) cleaning a base film: the polyacrylonitrile ultrafiltration membrane is used as a porous support membrane, and is placed in deionized water before use, and is subjected to vibration cleaning for a period of time until the surface of the membrane is flat and smooth;
(2) Preparing an oil phase solution: dissolving cyanuric chloride and trimesoyl chloride in a mixed solvent of cyclohexane and toluene (the mass ratio of cyanuric chloride to trimesoyl chloride is 1:1), preparing a solution with the mass concentration of an oil phase monomer of 0.5wt%, and accelerating the dissolution by ultrasound;
(3) Preparing an aqueous phase solution: resorcinol and sulfonated polyaniline (molecular weight: 5000) are dissolved in deionized water, the mass concentrations of the resorcinol and the sulfonated polyaniline are 3wt% and 0.5wt%, respectively, and likewise, the dissolution of the resorcinol and the sulfonated polyaniline is accelerated by ultrasound;
(4) Contacting one side surface of a polyacrylonitrile porous support membrane with an aqueous phase solution, standing for 2 minutes, and then sweeping to remove liquid drops on the surface of the membrane; then placing the oil phase solution on the surface of a polyacrylonitrile porous support film at the same side for 2 minutes, transferring the porous support film into a baking oven at 35 ℃ to carry out interfacial polymerization reaction on the adsorbed oil phase solution and the water phase solution for 20 minutes, and completing the interfacial polymerization reaction at the first stage; after the membrane is taken out, the surface of the membrane subjected to the interfacial polymerization reaction in the first stage is contacted with a sulfonated polyaniline solution with the mass concentration of 2wt% (the molecular weight of the sulfonated polyaniline is 5000), and the surface excess liquid is removed after the membrane is kept for 5 minutes; finally, the temperature is increased to 70 ℃ and maintained for 20 minutes, so that unreacted carbon-chlorine bonds on the surface of the membrane realize further grafting of sulfonated polyaniline, and the second-stage interfacial polymerization reaction is completed, thus preparing the renewable acid-resistant composite nanofiltration membrane.
Example 2
In this example, the process for preparing the regenerable acid-tolerant composite nanofiltration membrane was different from example 1 only in that the reducing agent solution treatment step was not performed, and the second stage interfacial polymerization reaction was performed by directly raising the temperature to 70 ℃ and maintaining for 20 minutes after the first stage interfacial polymerization reaction was completed.
Example 3
In this example, the preparation process of the regenerable acid-tolerant composite nanofiltration membrane is different from that of example 1 only in that the mass concentration of the aqueous phase monomer in the aqueous phase solution is 2wt%; the oil phase monomer is replaced by 2, 4-dichloro-1, 3, 5-triazine and isophthaloyl dichloride (the mass ratio of the 2, 4-dichloro-1, 3, 5-triazine to the isophthaloyl dichloride is 1:1.5), and the concentration of the oil phase monomer in the oil phase solution is 1wt%.
Example 4
In this example, the preparation process of the renewable acid-tolerant composite nanofiltration membrane is different from that of example 1 only in that the aqueous phase monomers are bisphenol fluorene (BHPF) and resorcinol, and the mass concentration ratio of the two aqueous phase solutions is 1:2; the mass concentration of the reducing agent solution used in the interfacial polymerization process was 3wt%.
Example 5
In this example, the process for preparing the regenerable acid-tolerant composite nanofiltration membrane differs from example 3 only in that the first stage temperature was 30℃for 5 minutes and the second stage temperature was 90℃for 10 minutes.
Example 6
In this example, the preparation process of the renewable acid-resistant composite nanofiltration membrane is different from that of example 1 only in that the reducing agent uses a sulfonated polyaniline compound having a number average molecular weight of 10000, and the mass concentration of the sulfonated polyaniline in the aqueous phase solution is 0.2wt%.
Example 7
In this embodiment, the preparation process of the renewable acid-tolerant composite nanofiltration membrane is the same as that of embodiment 1, except that the aqueous phase monomer is bisphenol fluorene (BHPF), 1-amino-5-naphthol, 1' -bi-2-naphthol, and the mass concentration ratio of the three in the aqueous phase solution is 1:1:1.
Comparative example 1
The preparation process of the nanofiltration membrane in the comparative example is different from that of the example 1 only in that cyanuric chloride is used as an oil phase monomer to prepare the membrane, the mass concentration of the oil phase monomer is kept to be 0.5wt%, and other parameters and the membrane preparation steps are unchanged.
Comparative example 2
The nanofiltration membrane preparation process in this comparative example differs from that of example 2 only in that the aqueous solution was free of the addition of the reducing agent sulfonated polyaniline.
Sample analysis
The SEM image of the surface of the regenerable acid-tolerant composite nanofiltration membrane prepared in example 1 is shown in fig. 1, and the membrane has a typical interfacial polymerization vesicle structure and is complete and defect-free in structure; the SEM image of the acid treated surface is shown in fig. 2, where the film structure is complete without significant changes.
The test conditions adopted in the invention are as follows: 200ppm potassium chromate solution, pH 1, temperature 25 ℃. The composite nanofiltration membrane was regenerated by reduction with a 100ppm sodium citrate solution for 30 minutes. The separation performance of the nanofiltration membranes prepared in examples 1 to 7 and comparative examples 1 to 2 is shown in Table 1.
TABLE 1 separation Properties of nanofiltration membranes produced in examples 1 to 7 and comparative examples 1 to 2
While the foregoing embodiments have been described in detail in connection with the embodiments of the invention, it should be understood that the foregoing embodiments are merely illustrative of the invention and are not intended to limit the invention, and any modifications, additions, substitutions and the like made within the principles of the invention are intended to be included within the scope of the invention.
Claims (8)
1. The preparation method of the renewable acid-resistant composite nanofiltration membrane is characterized by comprising the following steps of:
(1) Preparing an oil phase solution by taking an oil phase monomer as a raw material; the oil phase monomer comprises polybasic acyl chloride and a compound containing triazine ring groups;
(2) Preparing an aqueous phase solution by taking an aqueous phase monomer and a reducing agent as raw materials; the aqueous phase monomer is a phenolic compound, and the phenolic compound contains at least two hydroxyl groups or contains at least one hydroxyl group and amino group;
(3) The oil phase solution in the step (1) and the water phase solution in the step (2) are subjected to interfacial polymerization on a porous support membrane to obtain the renewable acid-resistant composite nanofiltration membrane;
the reducer is sulfonated polyaniline, and the number average molecular weight is between 500 and 10000;
in the step (3), the oil phase solution in the step (1) and the aqueous phase solution in the step (2) are subjected to a first-stage interfacial polymerization reaction and a second-stage interfacial polymerization reaction on the porous support membrane to obtain the renewable acid-resistant composite nanofiltration membrane; or, after the oil phase solution in the step (1) and the water phase solution in the step (2) are subjected to a first-stage interfacial polymerization reaction on the porous support membrane, treating the obtained membrane by using a reducing agent solution with the mass concentration of 2-8 and wt%, and continuing to perform a second-stage interfacial polymerization reaction to obtain the renewable acid-resistant composite nanofiltration membrane.
2. The method for preparing a renewable acid-tolerant composite nanofiltration membrane according to claim 1, wherein the polybasic acyl chloride comprises trimesoyl chloride or isophthaloyl dichloride; the compound containing triazine ring group comprises at least one of cyanuric chloride, 2, 4-dichloro-1, 3, 5-triazine or 2, 5-dichloro-1, 3, 5-triazine.
3. The method for preparing a renewable acid tolerant composite nanofiltration membrane according to claim 1, wherein the aqueous phase monomer comprises at least one of resorcinol, bisphenol fluorene, 1-amino-5-naphthol, or 1,1' -bi-2-naphthol.
4. The method for preparing the renewable acid-resistant composite nanofiltration membrane according to claim 1, wherein the mass concentration of the oil phase monomer in the oil phase solution is 0.5-5wt%; the mass ratio of the polybasic acyl chloride to the compound containing triazine ring group is 0.1-10:1.
5. The method for preparing the renewable acid-resistant composite nanofiltration membrane according to claim 1, wherein the mass concentration of the aqueous phase monomer in the aqueous phase solution is 2-8wt%, and the mass concentration of the reducing agent is 0.02-1 wt%.
6. The method for preparing the renewable acid-resistant composite nanofiltration membrane according to claim 1, wherein the interfacial polymerization reaction is carried out in two stages, wherein the parameters of the interfacial polymerization reaction in the first stage are reaction temperature of 20-40 ℃ and reaction time of 1-20 minutes; the parameters of the interfacial polymerization reaction in the second stage are the reaction temperature of 60-90 ℃ and the reaction time of 5-20 minutes.
7. The regenerable acid-tolerant composite nanofiltration membrane produced by the method of any one of claims 1-6.
8. The use of a renewable acid-tolerant composite nanofiltration membrane according to claim 7 in the field of wastewater treatment.
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